Organic light emitting device

ABSTRACT

An OLED comprising a hole-transporting layer and light-emitting layer wherein the hole-transporting layer comprises a hole-transporting polymer wherein no more than 5% of the polystyrene equivalent polymer weight measured by gel permeation chromatography consists of chains with weight of less than 50,000.

RELATED APPLICATIONS

This is a divisional patent application of U.S. application Ser. No.14/919,460, filed Oct. 21, 2015, which claims priority under 35 U.S.C. §119(a)-(d) or 365(b) to British application number 1418876.7, filed Oct.23, 2014; the entire contents of each is herein incorporated byreference.

BACKGROUND

Electronic devices containing active organic materials are attractingincreasing attention for use in devices such as organic light emittingdiodes (OLEDs), organic photoresponsive devices (in particular organicphotovoltaic devices and organic photosensors), organic transistors andmemory array devices. Devices containing active organic materials offerbenefits such as low weight, low power consumption and flexibility.Moreover, use of soluble organic materials allows use of solutionprocessing in device manufacture, for example inkjet printing orspin-coating.

An OLED may comprise a substrate carrying an anode, a cathode and one ormore organic light-emitting layers between the anode and cathode.

Holes are injected into the device through the anode and electrons areinjected through the cathode during operation of the device. Holes inthe highest occupied molecular orbital (HOMO) and electrons in thelowest unoccupied molecular orbital (LUMO) of a light-emitting materialcombine to form an exciton that releases its energy as light.

Suitable light-emitting materials include small molecule, polymeric anddendrimeric materials. Suitable light-emitting polymers includepoly(arylene vinylenes) such as poly(p-phenylene vinylenes) andpolyarylenes such as polyfluorenes.

A light emitting layer may comprise a semiconducting host material and alight-emitting dopant wherein energy is transferred from the hostmaterial to the light-emitting dopant. For example, J. Appl. Phys. 65,3610, 1989 discloses a host material doped with a fluorescentlight-emitting dopant (that is, a light-emitting material in which lightis emitted via decay of a singlet exciton).

Phosphorescent dopants are also known (that is, a light-emitting dopantin which light is emitted via decay of a triplet exciton).

US 2011/0198573 describes hole-transporting polymers with crosslinkablegroups.

JP 2007/204721 describes a method of fractionating an organic polymermaterial by bringing the organic polymer material into contact withporous particles.

It is an aim of the present invention to provide an OLED device with animproved properties for instance an improved device lifetime.

SUMMARY OF THE INVENTION

A first aspect of the present invention provides an OLED comprising ahole-transporting layer and light-emitting layer wherein thehole-transporting layer comprises a hole-transporting polymer wherein nomore than 5% of the polystyrene equivalent polymer weight measured bygel permeation chromatography consists of chains with a molecular weightof less than 50,000.

A second aspect of the present invention provides an OLED comprising ahole-transporting layer and light-emitting layer wherein thehole-transporting layer comprises a hole-transporting polymer having nomore than 10% of the polystyrene equivalent polymer weight measured bygel permeation chromatography consists of chains with a molecular weightof less than 100,000.

In a third aspect the invention provides an OLED comprising ahole-transporting layer and light-emitting layer wherein thehole-transporting layer comprises a hole-transporting polymer wherein nomore than 5% of the weight of the polymer consists of polymer chainswith a p/r ratio of less than about 100 wherein p/r is absolute polymerchain weight/average repeat unit weight.

A fourth aspect of the present invention provides a process for thepreparation of an OLED according to the first or second or third aspectof the invention, comprising the steps of:

(i) forming a hole-transporting layer which comprises ahole-transporting polymer; and

(ii) forming a light-emitting layer over the hole transporting layerwherein the light-emitting layer is formed by depositing a formulationcomprising the material or materials of said layer and at least onesolvent and evaporating the at least one solvent.

In a fifth aspect the invention provides a method of forming afractionated hole-transporting polymer comprising the step of separatinga low molecular weight fraction from a hole-transporting polymer.

The fractionated hole-transporting polymer of the fifth aspect may be asdescribed in any of the first, second and third aspects of theinvention.

As used herein, “molecular weight” is a weight in Daltons.

As used herein, “absolute polymer chain molecular weight” is an absolutemolecular weight of a polymer chain as measured by triple detection gelpermeation chromatography.

As used herein, “average repeat unit weight” is the mean averagemolecular mass in Daltons of repeat units of the polymer determined fromthe weights of monomers used to form the polymer and, in the case of apolymer comprising two or more repeat units having different weights,the proportions of the monomers.

A percentage of the polymer weight for a given molecular weight range asdescribed herein is the normalised cumulative height of the polymerweight distribution for that molecular weight range.

DESCRIPTION OF THE DRAWINGS

The invention will now be described in more detail with reference to thedrawings in which:

FIG. 1 illustrates schematically an OLED according to an embodiment ofthe invention;

FIG. 2 illustrates a polystyrene equivalent molecular weightdistribution plot measured by gel permeation chromatography of ahole-transporting polymer as described in the Comparative Example and acumulative height for this distribution;

FIG. 3 illustrates a polystyrene equivalent molecular weightdistribution plot measured by gel permeation chromatography of ahole-transporting polymer as described in Example 1 and a cumulativeheight for this distribution;

FIG. 4 illustrates an absolute molecular weight distribution plotmeasured by triple detection gel permeation chromatography of ahole-transporting polymer as described in the Comparative Example and acumulative height for this distribution;

FIG. 5 illustrates an absolute molecular weight distribution plotmeasured by triple detection gel permeation chromatography of ahole-transporting polymer as described in Example 1 and a cumulativeheight for this distribution; and

FIG. 6 illustrates a normalised luminance vs time plot comparingComparative Device 1 containing a hole-transporting layer formed fromthe Comparative Example polymer and Device Example 1 containing ahole-transporting layer formed from the polymer of Example 1

DETAILED DESCRIPTION

With reference to FIG. 1, an OLED 100 according to an embodiment of theinvention has an anode 101, a cathode 107, a light-emitting layer 105between the anode and the cathode, and a hole-transporting layer 103between the anode 101 and the light-emitting layer 105. The device issupported on a substrate 109, which may be a glass or plastic substrate.

One or more further layers may be provided between the anode and thecathode, for example a hole-injection layer, an electron-blocking layer,an electron-transporting layer or an electron blocking layer. In apreferred embodiment, a hole-injection layer is provided between theanode and the hole-transporting layer. Where present, the hole-injectionlayer is preferably adjacent to the hole-transporting layer. Preferably,the hole-transporting layer is adjacent to the light-emitting layer.

Light-emitting layer 105 may contain one or more fluorescentlight-emitting materials, one or more phosphorescent light-emittingmaterials or a combination of at least one fluorescent light-emittingmaterial and at least one phosphorescent light-emitting material.

The OLED may contain more than one light-emitting layer, for example aplurality of light-emitting layers that together produce white light.

Exemplary OLED layer structures include the following:

Anode/Hole transporting layer/Light-emitting layer/Cathode

Anode/Hole-injection layer/Hole-transporting layer/Light-emittinglayer/Cathode

Anode/Hole-injection layer/Hole-transporting layer/Light-emittinglayer/Electron-transporting layer/Cathode.

A first aspect of the present invention provides an OLED comprising ahole-transporting layer and light-emitting layer wherein thehole-transporting layer comprises a hole-transporting polymer wherein nomore than 5% of the polystyrene equivalent polymer weight measured bygel permeation chromatography consists of chains with a molecular weightof less than 50,000.

In a preferred embodiment of the first aspect of the invention, thehole-transporting layer comprises a hole-transporting polymer wherein nomore than 1% of the polystyrene equivalent polymer weight measured bygel permeation chromatography consists of polymer chains with amolecular weight of less than 50,000. Most preferably thehole-transporting layer comprises a hole-transporting polymer whereinless than 0.5% or less than 0.2% or less than 0.1% of the polystyreneequivalent polymer weight measured by gel permeation chromatographyconsists of polymer chains with a molecular weight of less than 50,000.

In a preferred embodiment of the first aspect of the invention, the holetransporting layer comprises a hole transporting polymer wherein no morethan 10% of the polystyrene equivalent polymer weight measured by gelpermeation chromatography consists of polymer chains with a molecularweight of less than 100,000. Preferably the hole-transporting layercomprises a hole-transporting polymer wherein no more than 5%, 4%, 3%,2% or 1% of the polystyrene equivalent polymer weight measured by gelpermeation chromatography consists of polymer chains with a molecularweight of less than 100,000.

A second aspect of the present invention provides an OLED comprising ahole-transporting layer and light-emitting layer wherein thehole-transporting layer comprises a hole-transporting polymer wherein nomore than 10% of the polystyrene equivalent polymer weight measured bygel permeation chromatography consists of polymer chains with amolecular weight of less than 100,000.

In a preferred embodiment of the second aspect of the invention, thehole transporting layer comprises a hole transporting polymer wherein nomore than 5% of the polystyrene equivalent polymer weight measured bygel permeation chromatography consists of polymer chains with amolecular weight of less than 100,000. Preferably the hole-transportinglayer comprises a hole-transporting polymer wherein no more than 4%, 3%,2% or 1% of the polystyrene equivalent polymer weight measured by gelpermeation chromatography consists of polymer chains with a molecularweight of less than 100,000.

In a preferred embodiment of the first and second aspects of theinvention, more than 20%, optionally more than 25%, of the polystyreneequivalent polymer weight measured by gel permeation chromatographyconsists of polymer chains with a molecular weight of at least 300,000.

In a third aspect the invention provides an OLED comprising ahole-transporting layer and light-emitting layer wherein thehole-transporting layer comprises a hole-transporting polymer wherein nomore than 5% of the weight of the polymer as measured by tripledetection gel permeation chromatography consists of polymer chains witha p/r ratio of less than about 50 wherein p/r is absolute polymer chainmolecular weight/average repeat unit molecular weight.

In a preferred embodiment of the third aspect, less than 4%, less than3%, less than 2% or less than 1% of the weight of the polymer asmeasured by triple detection gel permeation chromatography consists ofpolymer chains with a p/r ratio of less than about 50.

In a preferred embodiment of the third aspect, less than 10%, less than5%, less than 4%, less than 3%, less than 2% or less than 1% of theweight of the polymer as measured by triple detection gel permeationchromatography consists of polymer chains with a p/r ratio of less thanabout 100, preferably less than about 150.

In a preferred embodiment of the third aspect, more than 20%, optionallymore than 25% of the weight of the polymer as measured by tripledetection gel permeation chromatography consists of polymer chains witha p/r ratio of more than about 500.

In a preferred embodiment of the first, second or third aspect of theinvention, the hole-transporting layer comprises a hole-transportingpolymer having a polydispersity index of less than 4, preferably lessthan 3 or 2, most preferably about 1.5.

As used herein ‘polydispersity index’ refers to a polystyrene equivalentdispersity index as measured by gel permeation chromatography.

In a preferred embodiment of the first, second or third aspect of theinvention, the hole-transporting layer comprises a hole-transportingpolymer having a number-average molecular weight (Mn) in the range of5×10⁴, optionally 1×10⁵ up to 5×10⁵, and preferably in the range of2×10⁵ to 5×10⁵.

As used herein ‘number-average molecular weight’ refers to polystyreneequivalent number-average molecular weight as measured by gel permeationchromatography.

In a preferred embodiment of the first, second or third aspect of theinvention, the hole-transporting layer comprises a hole-transportingpolymer having a polystyrene equivalent weight average molecular weightas measured by gel permeation chromatography is in the range of 70,000or 1×10⁵ up to 1×10⁶, and preferably 2×10⁵ to 5×10⁵.

The hole-transporting layer may consist essentially of thehole-transporting polymer or may comprise one or more further materialsmixed with the hole-transporting polymer, for example one or morelight-emitting materials.

A fourth aspect of the invention provides a process for the preparationof an OLED according to the first, second or third aspect of theinvention, comprising the steps of:

-   -   (i) forming a hole-transporting layer which comprises a        hole-transporting polymer; and    -   (ii) forming a light-emitting layer over the hole-transporting        layer wherein the light-emitting layer is formed by depositing a        formulation comprising the material or materials of said layer        and at least one solvent and evaporating the at least one        solvent.

In a preferred embodiment of the fourth aspect of the invention, thehole-transporting layer is formed by depositing a formulation comprisingthe material or materials of said layer and at least one solvent andevaporating the at least one solvent. The hole-transporting polymer maybe soluble in one or more solvents used in step (ii) in forming thelight-emitting layer. Exemplary solvents that may be used to form thehole-transporting layer and/or the light-emitting layer, either alone orin combination, include substituted benzenes, for example benzenesubstituted with one or more C₁₋₁₀ alkyl or C₁₋₁₀ alkoxy groups such astoluene, xylene or anisole and mixtures thereof; benzene substitutedwith one or more chlorine groups; and tetrahydrofuran.

In a preferred embodiment of the fourth aspect of the invention, thehole-transporting layer is crosslinked prior to formation of thelight-emitting layer. Preferably, the hole-transporting polymer iscrosslinked by thermal treatment or by irradiation. Preferably, thehole-transporting polymer is crosslinked by thermal treatment. Thermalcrosslinking may be at a temperature in the range of about 80-250° C.,optionally about 80-200° C. or about 130-200° C.

The hole-transporting polymer preferably comprises one or more repeatunits substituted with a cross-linkable group. Preferably at least 1 mol% of the repeat units of the polymer comprise a crosslinkable group.More preferably at least 2, 3, 4, 5, 6, 7, 8 or 9 mol % of the repeatunits comprise a crosslinkable group. Most preferably at least 10 mol %of the repeat units comprise a crosslinkable group. Preferably, no morethan 25 mol % or no more than 20 mol % of the repeat units comprise acrosslinkable group.

A crosslinkable group is a group that may be crosslinked followingdeposition of a polymer to form a crosslinked layer prior to formationof a subsequent layer. For example the hole-transporting polymer may becrosslinked following deposition to form a crosslinked hole-transportinglayer prior to formation a subsequent layer which is typically thelight-emitting layer. Crosslinking can reduce the solubility of thepolymer in a solvent. Crosslinkable groups may be provided assubstituents of any repeat units of the polymer. End groups of thepolymer may be substituted with a crosslinkable group in addition to oras an alternative to crosslinkable groups provided as substituents ofrepeat units. Crosslinkable groups may be selected from:

-   -   an arylcyclobutene of formula (III):

wherein Sp is a spacer group, Ar is an aryl or heteroaryl group that maybe unsubstituted or substituted with one or more substituents; n=0 or 1,R independently in each occurrence is selected from H or a substituentand * is a point of attachment of the group of formula (III) to apolymeric repeat unit or end group;or

-   -   a group of formula (IV):

wherein Sp is a spacer group, n=0 or 1, R independently in eachoccurrence is H or a substituent, and * is a point of attachment of thegroup of formula (IV) to a polymeric repeat unit or end group.

Preferably, each R is selected from H and C₁₋₂₀ hydrocarbyl. Exemplaryhydrocarbyl groups are C₁₋₁₀ alkyl; phenyl; and phenyl substituted withone or more C₁₋₁₀ alkyl groups.

Preferably, R groups of formula (IV) are H.

Preferably, R groups of formula (III) are H or C₁₋₁₀ alkyl.

Preferably, Ar of formula (III) is benzene which may be unsubstituted orsubstituted, for example substituted with one or more C₁₋₁₀ alkylgroups.

Sp of formula (III) or (IV), if present, may be a C₁₋₂₀ alkyl groupwherein one or more non-adjacent C atoms are replaced with optionallysubstituted aryl or heteroaryl, O, S, C═O or —COO—, and one or more Hatoms may be replaced with F. Exemplary spacer groups are alkyl, alkoxy,phenylalkyl.

The hole-transporting polymer of the first, second or third aspect maybe a conjugated polymer comprising repeat units in the polymer backbonethat are conjugated together, or may be a non-conjugated polymer.

Preferably, the hole-transporting polymer is a conjugated polymer.Preferably, the conjugated polymer comprises repeat units comprisingarylene groups that are conjugated to arylene groups of adjacent repeatunits.

Exemplary hole-transporting polymers comprise a group of formula (V):

wherein Ar⁸ and Ar⁹ in each occurrence are independently selected fromsubstituted or unsubstituted aryl or heteroaryl, g is greater than orequal to 1, preferably 1 or 2, R¹³ is H, a substituent or a bond to apolymer backbone, and c and d are each independently 1, 2 or 3.

R¹³, which may be the same or different in each occurrence when g>1, ispreferably a substituent and is more preferably selected from the groupconsisting of alkyl, for example C₁₋₂₀ alkyl, Ar¹⁰, or a branched orlinear chain of Ar¹⁰ groups, wherein Ar¹⁰ in each occurrence isindependently optionally substituted aryl or heteroaryl. Exemplarygroups R¹³ are C₁₋₂₀ alkyl, phenyl and phenyl substituted with one ormore C₁₋₂₀ alkyl groups.

Any of Ar⁸, Ar⁹ and, if present, Ar¹⁰ bound directly to a N atom in therepeat unit of formula (V) may be linked by a direct bond or a divalentlinking atom or group to another of Ar⁸, Ar⁹ and Ar¹⁰ bound directly tothe same N atom. Preferred divalent linking atoms and groups include O,S; substituted N; and substituted C.

Any of Ar⁸, Ar⁹ and, if present, Ar¹⁰ may be substituted with one ormore substituents. Exemplary substituents are substituents R¹⁴, whereineach R¹⁴ may independently be selected from the group consisting ofsubstituted or unsubstituted alkyl, optionally C₁₋₂₀ alkyl, wherein oneor more non-adjacent C atoms may be replaced with optionally substitutedaryl or heteroaryl, O, S, substituted N, C═O or —COO— and one or more Hatoms may be replaced with F.

Substituted N or substituted C, where present, may be N or C substitutedwith a hydrocarbyl group (in the case of substituted N) or twohydrocarbyl groups (in the case of substituted C), for example a C₁₋₁₀alkyl, unsubstituted phenyl or phenyl substituted with one or more C₁₋₁₀alkyl groups.

A group of formula (V) may be provided in the main chain of a conjugatedpolymer in which case it may be a repeat unit of formula (Va):

wherein Ar⁸, Ar⁹, R¹³, c and d are as defined above for formula (V).

A group of formula (V) may be a side-group of a conjugated ornon-conjugated polymer comprising repeat units of formula (VII):

wherein RU is a backbone repeat unit, for example a homopolymerconsisting of or a copolymer comprising repeat units of formula group offormula (VIIa):

Preferred repeat units of formula (Va) have sub-formulae 1-3:

Preferably, Ar⁸ and Ar¹⁰ of repeat units of formula 1 are phenyl and Ar⁹is phenyl or a polycyclic aromatic group. More preferably Ar⁹, mostpreferably the central Ar⁹ group of formula 1 bound directly to two Natoms is a C₁₀₋₂₀ polycyclic aromatic, optionally an optionallysubstituted fluorene, for example as described in WO 2005/049546 and WO2013/108022 the contents of which are incorporated by reference.

In one preferred arrangement, R¹³ is Ar¹⁰ and each of Ar⁸, Ar⁹ and Ar¹⁰are independently unsubstituted or substituted with one or more C₁₋₂₀alkyl groups.

In a preferred arrangement, Ar⁸, Ar⁹ and Ar¹⁰ are phenyl, each of whichmay independently be substituted with one or more substituents asdescribed above.

In another preferred arrangement, Ar⁸ and Ar⁹ are phenyl, each of whichmay be substituted with one or more C₁₋₂₀ alkyl groups, and R¹³ is3,5-diphenylbenzene wherein each phenyl may be substituted with one ormore C₁₋₂₀ alkyl groups.

In another preferred arrangement, c, d and g are each 1 and Ar⁸ and Ar⁹are phenyl linked by an oxygen atom to form a phenoxazine ring.

Amine repeat units may be provided in a molar amount in the range ofabout 0.5 mol % up to about 50 mol %, optionally up to 40 mol %.

Hole-transporting polymers as described herein may be homopolymers, forexample homopolymers of a repeat unit comprising a group of formula (V),or may be copolymers comprising one or more co-repeat units.

Exemplary co-repeat units include arylene repeat units, for example1,2-, 1,3- and 1,4-phenylene repeat units, 3,6- and 2,7-linked fluorenerepeat units, indenofluorene, naphthalene, anthracene and phenanthrenerepeat units, each of which may be unsubstituted or substituted with oneor more substituents. Substituents may be selected from groups R⁷described below.

One preferred class of arylene repeat units is phenylene repeat units,such as phenylene repeat units of formula (X):

wherein w in each occurrence is independently 0, 1, 2, 3 or 4,optionally 1 or 2; n is 1, 2 or 3; and R⁷ independently in eachoccurrence is a substituent.

Where present, each R⁷ may independently be selected from the groupconsisting of:

-   -   alkyl, optionally C₁₋₂₀ alkyl, wherein one or more non-adjacent        C atoms may be replaced with optionally substituted aryl or        heteroaryl, O, S, substituted N, C═O or —COO—, and one or more H        atoms may be replaced with F;    -   aryl and heteroaryl groups that may be unsubstituted or        substituted with one or more substituents, preferably phenyl        substituted with one or more C₁₋₂₀ alkyl groups;    -   a linear or branched chain of aryl or heteroaryl groups, each of        which groups may independently be substituted, for example a        group of formula —(Ar³)_(r) wherein each Ar³ is independently an        aryl or heteroaryl group and r is at least 2, preferably a        branched or linear chain of phenyl groups each of which may be        unsubstituted or substituted with one or more C₁₋₂₀ alkyl        groups; and    -   a crosslinkable-group, for example a group, optionally a group        of formula (III) or (IV).

Substituted N, where present, may be —NR²— wherein R² is C₁₋₂₀ alkyl;unsubstituted phenyl; or phenyl substituted with one or more C₁₋₂₀ alkylgroups.

Preferably, each R⁷ is independently selected from C₁₋₄₀ hydrocarbyl,and is more preferably selected from C₁₋₂₀ alkyl; unsubstituted phenyl;and phenyl substituted with one or more C₁₋₂₀ alkyl groups; a linear orbranched chain of phenyl groups, wherein each phenyl may beunsubstituted or substituted with one or more substituents; and acrosslinkable group.

If n is 1 then exemplary repeat units of formula (X) include thefollowing:

A particularly preferred repeat unit of formula (X) has formula (Xa):

Substituents R⁷ of formula (Xa) are adjacent to linking positions of therepeat unit, which may cause steric hindrance between the repeat unit offormula (Xa) and adjacent repeat units, resulting in the repeat unit offormula (Xa) twisting out of plane relative to one or both adjacentrepeat units.

Exemplary repeat units where n is 2 or 3 include the following:

A preferred repeat unit has formula (Xb):

The two R⁷ groups of formula (Xb) may cause steric hindrance between thephenyl rings they are bound to, resulting in twisting of the two phenylrings relative to one another.

A further class of arylene repeat units is optionally substitutedfluorene repeat units, such as repeat units of formula (XI):

wherein R⁸ in each occurrence is the same or different and is asubstituent wherein the two groups R⁸ may be linked to form a ring; R⁷is a substituent as described above; and d is 0, 1, 2 or 3.

Each R⁸ may independently be selected from the group consisting of:

-   -   alkyl, optionally C₁₋₂₀ alkyl, wherein one or more non-adjacent        C atoms may be replaced with optionally substituted aryl or        heteroaryl, O, S, substituted N, C═O or —COO—, and one or more H        atoms may be replaced with F;    -   aryl and heteroaryl groups that may be unsubstituted or        substituted with one or more substituents, preferably phenyl        substituted with one or more C₁₋₂₀ alkyl groups; and    -   a linear or branched chain of aryl or heteroaryl groups, each of        which groups may independently be substituted, for example a        group of formula —(Ar⁷)_(r) wherein each Ar⁷ is independently an        aryl or heteroaryl group and r is at least 2, optionally 2 or 3,        preferably a branched or linear chain of phenyl groups each of        which may be unsubstituted or substituted with one or more C₁₋₂₀        alkyl groups.    -   a crosslinkable-group, optionally a group of formula (III) or        (IV).

Preferably, each R⁸ is independently a C₁₋₄₀ hydrocarbyl group.

Different groups R⁸ are disclosed in WO 2012/104579 the contents ofwhich are incorporated in entirety by reference.

Substituted N, where present, may be —NR²— wherein R² is as describedabove.

Exemplary substituents R⁷ are alkyl, for example C₁₋₂₀ alkyl, whereinone or more non-adjacent C atoms may be replaced with O, S, C═O and—COO—, optionally substituted aryl, optionally substituted heteroaryl,alkoxy, alkylthio, fluorine, cyano and arylalkyl. Particularly preferredsubstituents include C₁₋₂₀ alkyl and substituted or unsubstituted aryl,for example phenyl. Optional substituents for the aryl include one ormore C₁₋₂₀ alkyl groups.

The extent of conjugation of repeat units of formula (XI) to aryl orheteroaryl groups of adjacent repeat units in the polymer backbone maybe controlled by (a) linking the repeat unit through the 3- and/or6-positions to limit the extent of conjugation across the repeat unit,and/or (b) substituting the repeat unit with one or more substituents R⁸in or more positions adjacent to the linking positions in order tocreate a twist with the adjacent repeat unit or units, for example a2,7-linked fluorene carrying a C₁₋₂₀ alkyl substituent in one or both ofthe 3- and 6-positions.

The repeat unit of formula (XI) may be a 2,7-linked repeat unit offormula (XIa):

Optionally, the repeat unit of formula (XIa) is not substituted in aposition adjacent to the 2- or 7-position. A relatively high degree ofconjugation across the repeat unit of formula (XIa) may be provided inthe case where each d=0, or where any substituent R⁷ is not present at aposition adjacent to the linking 2- or 7-positions of formula (XIa).

Conjugation across the repeat unit of formula (XIa) may be limited inthe case where at least one d is at least 1, and where at least onesubstituent R⁷ is present at a position adjacent to the linking 2- or7-positions of formula (XIa). Optionally, each d is 1 and the 3- and/or6-position of the repeat unit of formula (XIa) is substituted with asubstituent R⁷ to provide a relatively low degree of conjugation acrossthe repeat unit. Substitutions at the 3- and/or 6-positions is disclosedin WO 2013/191086 the contents of which are incorporated herein byreference.

The repeat unit of formula (XI) may be a 3,6-linked repeat unit offormula (XIb)

The extent of conjugation across a repeat unit of formula (XIb) may berelatively low as compared to a corresponding repeat unit of formula(XIa).

Another exemplary arylene repeat unit has formula (VIII):

wherein R⁷, R⁸ and d are as described with reference to formulae (X) and(XI) above. Any of the R⁷ groups may be linked to any other of the R⁷groups to form a ring. The ring so formed may be unsubstituted or may besubstituted with one or more substituents, optionally one or more C₁₋₂₀alkyl groups.

Repeat units of formula (VIII) may have formula (VIIIa) or (VIIIb):

The one or more co-repeat units may include a conjugation-breakingrepeat unit, which is a repeat unit that does not provide anyconjugation path between repeat units adjacent to theconjugation-breaking repeat unit.

Polymers as described herein are suitably amorphous

Polymer Synthesis

One method of forming conjugated hole-transporting polymers as describedherein is Suzuki polymerisation, for example as described in WO 00/53656or U.S. Pat. No. 5,777,070 which allows formation of C—C bonds betweentwo aromatic or heteroaromatic groups, and so enables formation ofpolymers having conjugation extending across two or more repeat units.Suzuki polymerisation takes place in the presence of a palladium complexcatalyst and a base.

As illustrated in Scheme 1, in the Suzuki polymerisation process amonomer for forming repeat units RU1 has two leaving groups LG1 such asboronic acid or boronic ester group bound to the same or differentarylene or heteroarylene groups of RU1, and a monomer for forming repeatunits RU2 has two leaving groups LG2 such as halogen, sulfonic acid orsulfonic ester bound to the same or different arylene or heteroarylenegroups of RU1. The monomers are polymerised to form a carbon-carbon bondbetween arylene or heteroarylene groups of RU 1 and RU 2:

Exemplary boronic esters have formula (VI):

wherein R⁶ in each occurrence is independently a C₁₋₂₀ alkyl group, *represents the point of attachment of the boronic ester to an aromaticring of the monomer, and the two groups R⁶ may be linked to form a ring.In a preferred embodiment, the two groups R⁶ are linked to form thepinacol ester of boronic acid:

It will be understood by the skilled person that a monomer LG1-RU1-LG1will not polymerise to form a direct carbon-carbon bond with anothermonomer LG1-RU1-LG1. A monomer LG2-RU2-LG2 will not polymerise to form adirect carbon-carbon bond with another monomer LG2-RU2-LG2.

Preferably, one of LG1 and LG2 is bromine or iodine and the other is aboronic acid or boronic ester.

This selectivity means that the ordering of repeat units in the polymerbackbone can be controlled such that all or substantially all RU1 repeatunits formed by polymerisation of LG1-RU1-LG1 are adjacent, on bothsides, to RU2 repeat units.

In the example of Scheme 1 above, an AB copolymer is formed bycopolymerisation of two monomers in a 1:1 ratio, however it will beappreciated that more than two or more than two monomers may be used inthe polymerisation, and any ratio of monomers may be used.

In the example of Scheme 1 above, a linear copolymer is formed. In otherembodiments, one or more monomers may contain 3 or more leaving groupsto form a branching polymer.

The base may be an organic or inorganic base. Exemplary organic basesinclude tetra-alkylammonium hydroxides, carbonates and bicarbonates.Exemplary inorganic bases include metal (for example alkali or alkaliearth) hydroxides, carbonates and bicarbonates.

The palladium complex catalyst may be a palladium (0) or palladium (II)compound.

Particularly preferred catalysts aretetrakis(triphenylphosphine)palladium (0) and palladium (II) acetatemixed with a phosphine.

A phosphine may be provided, either as a ligand of the palladiumcompound catalyst or as a separate compound added to the polymerisationmixture. Exemplary phosphines include triarylphosphines, for exampletriphenylphosphines wherein each phenyl may independently beunsubstituted or substituted with one or more substituents, for exampleone or more C₁₋₅ alkyl or C₁₋₅ alkoxy groups.

Particularly preferred are triphenylphospine andtris(ortho-methoxytriphenyl) phospine.

A further polymerisation method is Yamamoto polymerisation in whichmonomers carrying halogen (preferably bromine) leaving groups react inthe presence of a nickel catalyst.

The polymerisation reaction may take place in a single organic liquidphase in which all components of the reaction mixture are soluble. Thereaction may take place in a two-phase aqueous-organic system, in whichcase a phase transfer agent may be used. The reaction may take place inan emulsion formed by mixing a two-phase aqueous-organic system with anemulsifier.

The polymer may be end-capped by addition of an endcapping reactant.Suitable end-capping reactants are aromatic or heteroaromatic materialssubstituted with only one leaving group. The end-capping reactants mayinclude reactants substituted with a halogen for reaction with a boronicacid or boronic ester group at a polymer chain end, and reactantssubstituted with a boronic acid or boronic ester for reaction with ahalogen at a polymer chain end. Exemplary end-capping reactants arehalobenzenes, for example bromobenzene, and phenylboronic acid.End-capping reactants may be added during or at the end of thepolymerisation reaction.

After polymer synthesis the hole-transporting polymer may be modified toprovide a polymer having a molecular weight as described in the first orsecond aspects of the invention.

The polymer molecular weight may be fractionated by filtration through asize exclusion membrane.

Preferred methods of fractionation include selective precipitation orchromatographic methods such as preparative size exclusionchromatography. Most preferably the fractionation is by selectiveprecipitation.

Selective precipitation is a method in which a polymer is dissolved inone or more solvents. A solvent or solvent mixture in which the polymeris less soluble is added to the polymer solution to precipitate thepolymer. Higher molecular weight polymer chains are selectivelyprecipitated and therefore the precipitated solid is depleted of lowermolecular weight polymer chains.

Light-Emitting Layers

An OLED may contain one or more light-emitting layers. Suitablelight-emitting materials for a light-emitting layer include polymeric,small molecule and dendrimeric light-emitting materials, each of whichmay be fluorescent or phosphorescent.

A light-emitting layer of an OLED may be unpatterned, or may bepatterned to form discrete pixels. Each pixel may be further dividedinto subpixels. The light-emitting layer may contain a singlelight-emitting material, for example for a monochrome display or othermonochrome device, or may contain materials emitting different colours,in particular red, green and blue light-emitting materials for afull-colour display.

A light-emitting layer may contain a mixture of more than onelight-emitting material, for example a mixture of light-emittingmaterials that together provide white light emission.

A blue light emitting material may have a photoluminescent spectrum witha peak in the range of 400-490 nm.

A green light emitting material may have a photoluminescent spectrumwith a peak in the range of more than 490 nm up to 580 nm.

A red light emitting material may optionally have a peak in itsphotoluminescent spectrum of more than 580 nm up to 650 nm, preferably600-630 nm.

Exemplary fluorescent polymeric light-emitting materials includepolymers comprising one or more of arylene repeat units, arylenevinylene repeat units and arylamine repeat units. A fluorescentlight-emitting layer may consist of a light-emitting material alone ormay further comprise one or more further materials mixed with thelight-emitting material. Exemplary further materials may be selectedfrom hole-transporting materials; electron-transporting materials andtriplet-accepting materials, for example a triplet-accepting polymer asdescribed in WO 2013/114118, the contents of which are incorporatedherein by reference.

Preferred light-emitting polymers are copolymers comprising one or morearylene repeat units selected from formulae (X), (XI) and (VIII) and (V)described above with reference to the hole-transporting polymer;phenanthrene repeat units; naphthalene repeat units; anthracene repeatunits; and perylene repeat units. Each of these repeat units may belinked to adjacent repeat units through any two of the aromatic carbonatoms of these units. Specific exemplary linkages include9,10-anthracene; 2,6-anthracene; 1,4-naphthalene; 2,6-naphthalene;2,7-phenanthrene; and 2,5-perylene. Each of these repeat units may besubstituted or unsubstituted, for example substituted with one or moreC₁₋₄₀ hydrocarbyl groups.

Exemplary phosphorescent light-emitting materials include metalcomplexes comprising substituted or unsubstituted complexes of formula(IX):ML ¹ _(q) L ² _(r) L ³ _(s)  (IX)wherein M is a metal; each of L¹, L² and L³ is a coordinating group; qis an integer; r and s are each independently 0 or an integer; and thesum of (a. q)+(b. r)+(c.s) is equal to the number of coordination sitesavailable on M, wherein a is the number of coordination sites on L¹, bis the number of coordination sites on L² and c is the number ofcoordination sites on L³. Preferably, a, b and c are each 1 or 2.Preferably, a, b and c are each 2 (bidentate ligands). Preferably, q is2 or 3 and r and s are 0 or 1.

Heavy elements M induce strong spin-orbit coupling to allow rapidintersystem crossing and emission from triplet or higher states.Suitable heavy metals M include d-block metals, in particular those inrows 2 and 3 i.e. elements 39 to 48 and 72 to 80, in particularruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum andgold. Iridium is particularly preferred.

Exemplary ligands L¹, L² and L³ include carbon or nitrogen donors suchas porphyrin or bidentate ligands of formula (I):

wherein Ar⁵ and Ar⁶ may be the same or different and are independentlyselected from substituted or unsubstituted aryl or heteroaryl; X¹ and Y¹may be the same or different and are independently selected from carbonor nitrogen; and Ar⁵ and Ar⁶ may be fused together. Ligands wherein X¹is carbon and Y¹ is nitrogen are preferred, in particular ligands inwhich Ar⁵ is a single ring or fused heteroaromatic of N and C atomsonly, for example pyridyl or isoquinoline, and Ar⁶ is a single ring orfused aromatic, for example phenyl or naphthyl.

Examples of bidentate ligands are illustrated below:

Each of Ar⁵ and Ar⁶ may carry one or more substituents. Two or more ofthese substituents may be linked to form a ring, for example an aromaticring.

Other ligands suitable for use with d-block elements includediketonates, in particular acetylacetonate (acac); triarylphosphines andpyridine, each of which may be substituted.

Exemplary substituents include groups R⁷ as described above withreference to Formula (X). Particularly preferred substituents includefluorine or trifluoromethyl which may be used to blue-shift the emissionof the complex, for example as disclosed in WO 02/45466, WO 02/44189, US2002-117662 and US 2002-182441; alkyl or alkoxy groups, for exampleC₁₋₂₀ alkyl or alkoxy, which may be as disclosed in JP 2002-324679;carbazole which may be used to assist hole transport to the complex whenused as an emissive material, for example as disclosed in WO 02/81448;bromine, chlorine or iodine which can serve to functionalise the ligandfor attachment of further groups, for example as disclosed in WO02/68435 and EP 1245659; and dendrons which may be used to obtain orenhance solution processability of the metal complex, for example asdisclosed in WO 02/66552.

A light-emitting dendrimer typically comprises a light-emitting corebound to one or more dendrons, wherein each dendron comprises abranching point and two or more dendritic branches. Preferably, thedendron is at least partially conjugated, and at least one of thebranching points and dendritic branches comprises an aryl or heteroarylgroup, for example a phenyl group. In one arrangement, the branchingpoint group and the branching groups are all phenyl, and each phenyl mayindependently be substituted with one or more substituents, for examplealkyl or alkoxy.

A dendron may have optionally substituted formula (II)

wherein BP represents a branching point for attachment to a core and G₁represents first generation branching groups.

The dendron may be a first, second, third or higher generation dendron.G₁ may be substituted with two or more second generation branchinggroups G₂, and so on, as in optionally substituted formula (IIa):

wherein u is 0 or 1; v is 0 if u is 0 or may be 0 or 1 if u is 1; BPrepresents a branching point for attachment to a core and G₁, G₂ and G₃represent first, second and third generation dendron branching groups.In one preferred embodiment, each of BP and G₁, G₂ . . . G_(n) isphenyl, and each phenyl BP, G₁, G₂ . . . G_(n-1) is a 3,5-linked phenyl.

A preferred dendron is a substituted or unsubstituted dendron of formula(IIb):

wherein * represents an attachment point of the dendron to a core.

BP and/or any group G may be substituted with one or more substituents,for example one or more C₁₋₂₀ alkyl or alkoxy groups.

Phosphorescent light-emitting materials may be provided in alight-emitting layer with a host material. The host preferably has atriplet energy level that is no more than 0.1 eV lower than that of thephosphorescent light-emitting material, more preferably a triplet energylevel that the same as or higher than that of the phosphorescentlight-emitting material.

Suitable host materials include small molecule, dendrimeric andpolymeric host materials. Polymeric host materials includenon-conjugated polymers with pendant charge-transporting groups, forexample polyvinylcarbazole, and at least partially conjugated polymers,for example polymers comprising one or both of arylene repeat units andamine repeat units, for example arylene repeat units of formula (X),(XI) and (VIII) and amine repeat units of formula (V).

Phosphorescent light-emitting materials may make up about 0.05 mol % upto about 20 mol %, optionally about 0.1-10 mol % of ahost/phosphorescent light-emitting material composition.

The phosphorescent light-emitting material may be physically mixed withthe host material or may be covalently bound thereto. In the case of apolymeric host, the phosphorescent light-emitting material may beprovided in a side-chain, main chain or end-group of the polymer. Wherethe phosphorescent material is provided in a polymer side-chain, thephosphorescent material may be directly bound to the backbone of thepolymer or spaced apart therefrom by a spacer group, for example a C₁₋₂₀alkyl spacer group in which one or more non-adjacent C atoms may bereplaced by O or S.

The hole-transporting layer as described herein may be non-emissive whenthe device is in use, or may emit light in which case thehole-transporting layer may contain a light-emitting material asdescribed herein bound to the hole-transporting polymer or mixed withthe hole-transporting polymer.

Hole Injection Layers

A conductive hole injection layer, which may be formed from a conductiveorganic or inorganic material, may be provided between the anode and thelight-emitting layer or layers of an OLED to improve hole injection fromthe anode into the layer or layers of semiconducting polymer. Examplesof doped organic hole injection materials include optionallysubstituted, doped poly(ethylene dioxythiophene) (PEDT), in particularPEDT doped with a charge-balancing polyacid such as polystyrenesulfonate (PSS) as disclosed in EP 0901176 and EP 0947123, polyacrylicacid or a fluorinated sulfonic acid, for example Nafion®; polyaniline asdisclosed in U.S. Pat. No. 5,723,873 and U.S. Pat. No. 5,798,170; andoptionally substituted polythiophene or poly(thienothiophene). Examplesof conductive inorganic materials include transition metal oxides suchas VOx MoOx and RuOx as disclosed in Journal of Physics D: AppliedPhysics (1996), 29(11), 2750-2753.

Where a hole-transporting layer is present, a hole-injection layer maybe provided between the anode and the hole-transporting layer.

Charge Transporting and Charge Blocking Layers

A hole transporting layer may be provided between the anode and thelight-emitting layer or layers, as described above. Likewise, anelectron transporting layer may be provided between the cathode and thelight-emitting layer or layers.

Similarly, an electron blocking layer may be provided between the anodeand the light-emitting layer and a hole blocking layer may be providedbetween the cathode and the light-emitting layer. Transporting andblocking layers may be used in combination. Depending on its HOMO andLUMO levels, a single layer may both transport one of holes andelectrons and block the other of holes and electrons.

The hole transporting layer preferably has a HOMO level of less than orequal to 5.5 eV, more preferably around 4.8-5.5 eV as measured by cyclicvoltammetry. The HOMO level of the hole transport layer may be selectedso as to be within 0.2 eV, optionally within 0.1 eV, of an adjacentlayer (such as a light-emitting layer) in order to provide a smallbarrier to hole transport between these layers. The hole-transportinglayer may be a polymer comprising repeat units of formula (I) asdescribed above.

If present, an electron transporting layer located between thelight-emitting layers and cathode preferably has a LUMO level of around2.5-3.5 eV as measured by cyclic voltammetry. For example, a layer of asilicon monoxide or silicon dioxide or other thin dielectric layerhaving thickness in the range of 0.2-2 nm may be provided between thelight-emitting layer nearest the cathode and the cathode. HOMO and LUMOlevels may be measured using cyclic voltammetry.

An electron transporting layer may contain a polymer comprising a chainof optionally substituted arylene repeat units, such as a chain offluorene repeat units.

Cathode

The cathode is selected from materials that have a work functionallowing injection of electrons into the light-emitting layer. Otherfactors influence the selection of the cathode such as the possibilityof adverse interactions between the cathode and the light-emittingmaterial. The cathode may consist of a single material such as a layerof aluminium. Alternatively, it may comprise a plurality of conductivematerials, for example a plurality of conductive metals such a bilayerof a low work function material and a high work function material suchas calcium and aluminium as disclosed in WO 98/10621. The cathode maycomprise a layer of elemental barium, for example as disclosed in WO98/57381, Appl. Phys. Lett. 2002, 81(4), 634 and WO 02/84759. Thecathode may comprise a thin (e.g. less than 5 nm) layer of metalcompound between the organic semiconducting layers and one or moreconductive cathode layers, in particular an oxide or fluoride of analkali or alkali earth metal, to assist electron injection, for examplelithium fluoride, for example as disclosed in WO 00/48258; bariumfluoride, for example as disclosed in Appl. Phys. Lett. 2001, 79(5),2001; and barium oxide. In order to provide efficient injection ofelectrons into the device, the cathode preferably has a work function ofless than 3.5 eV, more preferably less than 3.2 eV, most preferably lessthan 3 eV. Work functions of metals can be found in, for example,Michaelson, J. Appl. Phys. 48(11), 4729, 1977.

The cathode may be opaque or transparent. Transparent cathodes areparticularly advantageous for active matrix devices because emissionthrough a transparent anode in such devices is at least partiallyblocked by drive circuitry located underneath the emissive pixels. Atransparent cathode comprises a layer of an electron injecting materialthat is sufficiently thin to be transparent. Typically, the lateralconductivity of this layer will be low as a result of its thinness. Inthis case, the layer of electron injecting material is used incombination with a thicker layer of transparent conducting material suchas indium tin oxide.

It will be appreciated that a transparent cathode device need not have atransparent anode (unless, of course, a fully transparent device isdesired), and so the transparent anode used for bottom-emitting devicesmay be replaced or supplemented with a layer of reflective material suchas a layer of aluminium. Examples of transparent cathode devices aredisclosed in, for example, GB 2348316.

Encapsulation

Organic optoelectronic devices tend to be sensitive to moisture andoxygen. Accordingly, the substrate preferably has good barrierproperties for prevention of ingress of moisture and oxygen into thedevice. The substrate is commonly glass, however alternative substratesmay be used, in particular where flexibility of the device is desirable.For example, the substrate may comprise one or more plastic layers, forexample a substrate of alternating plastic and dielectric barrier layersor a laminate of thin glass and plastic.

The device may be encapsulated with an encapsulant (not shown) toprevent ingress of moisture and oxygen. Suitable encapsulants include asheet of glass, films having suitable barrier properties such as silicondioxide, silicon monoxide, silicon nitride or alternating stacks ofpolymer and dielectric or an airtight container. In the case of atransparent cathode device, a transparent encapsulating layer such assilicon monoxide or silicon dioxide may be deposited to micron levels ofthickness, although in one preferred embodiment the thickness of such alayer is in the range of 20-300 nm. A getter material for absorption ofany atmospheric moisture and/or oxygen that may permeate through thesubstrate or encapsulant may be disposed between the substrate and theencapsulant.

Formulation Processing

A formulation suitable for forming the hole-transporting layer and thelight-emitting layer may be formed from the components forming thoselayers and one or more suitable solvents.

The formulation may be a solution of the components of the layer inquestion, or may be a dispersion in the one or more solvents in whichone or more components are not dissolved. Preferably, the formulation isa solution.

Particularly preferred solution deposition techniques including printingand coating techniques such spin-coating and inkjet printing.

Coating methods are particularly suitable for devices wherein patterningof the light-emitting layer is unnecessary—for example for lightingapplications or simple monochrome segmented displays.

Printing methods are particularly suitable for high information contentdisplays, in particular full colour displays. A device may be inkjetprinted by providing a patterned layer over the anode and defining wellsfor printing of one colour (in the case of a monochrome device) ormultiple colours (in the case of a multicolour, in particular fullcolour device). The patterned layer is typically a layer of photoresistthat is patterned to define wells as described in, for example, EP0880303.

As an alternative to wells, the ink may be printed into channels definedwithin a patterned layer. In particular, the photoresist may bepatterned to form channels which, unlike wells, extend over a pluralityof pixels and which may be closed or open at the channel ends.

Other solution deposition techniques include dip-coating, slot diecoating, roll printing and screen printing.

For the avoidance of doubt, insofar as is practicable any embodiment oraspect of the invention may occur in combination with any otherembodiment or aspect of the invention.

EXAMPLE

Comparative Hole-Transporting Polymer

A hole-transporting polymer was formed by Suzuki polymerisation asdescribed in WO 00/53656 comprising:

-   -   50 mol % of a repeat unit of formula (XIa) wherein R⁷ is methyl        in each case, d=1 in each case and R⁸ is a substituent as        described in the description;    -   40 mol % of a repeat unit of formula (V) sub-formula 1 wherein        the central Ar⁹ group linked to two N atoms is substituted        fluorene and Ar¹⁰ is phenyl in both occurrences and the        remaining Ar groups are phenylene as described in the        description.    -   10 mol % of a crosslinkable repeat unit of formula (XIa).

The average repeat unit molecular weight of the polymer is about 600 Da.

The polymer was analysed by gel permeation chromatography and thepolystyrene-equivalent weight-average molecular weight (Mw) of thepolymer was 317,000, the polystyrene-equivalent number-average molecularweight (Mn) was 55,000 and the polystyrene-equivalent polydispersityindex was 5.7. A polystyrene equivalent weight distribution plot of thispolymer measured by gel permeation chromatography is shown in FIG. 2. Anabsolute molecular weight distribution plot of this polymer measured bytriple detection gel permeation chromatography is shown in FIG. 4

Hole-Transporting Polymer Example 1

The comparative polymer described in the example above was fractionatedby selective precipitation. The comparative polymer was dissolved intoluene and added dropwise to isopropyl alcohol. The resultant solid orgel was separated from the solvents and the process was repeated afurther two times to provide a polymer with optimised molecular weightdistributions.

The polymer was analysed by gel permeation chromatography and thepolystyrene-equivalent weight-average molecular weight (Mw) of thepolymer was 523,000, the polystyrene-equivalent number-average molecularweight (Mn) was 350,000 and the polystyrene-equivalent polydispersityindex was 1.5. A polystyrene equivalent weight distribution plot of thispolymer measured by gel permeation chromatography is shown in FIG. 3. Anabsolute molecular weight distribution plot of this polymer measured bytriple detection gel permeation chromatography is shown in FIG. 5

The proportions by weight of polymer chains making up differentpolystyrene equivalent molecular weight ranges of the total polymerweight as measured by GPC are set out in Table 1.

Proportions for Comparative Polymer 1 and Polymer Example 1 are takenfrom the normalised cumulative heights shown in FIGS. 2 and 3respectively. Height measurements were taken at a data rate of 1 Hz, andsummed and normalised using Cirrus software available from Agilent.

TABLE 1 Comparative Polymer 1 Polymer Example 1 Molecular Proportion oftotal Proportion of total weight polymer weight by GPC polymer weight byGPC range (%) (%)  <30k 9.05 0  30-50k 4.29 0.05  50-100k 12.45 0.78100-300k 37.77 29.45 300-500k 16.91 30.99 500-1000k 14.49 28.60 >1000k5.04 10.14

The proportions by molecular weight of polymer chains making updifferent weight ranges of the total polymer weight as measured bytriple detection GPC are set out in Table 2.

Proportions for Comparative Polymer 1 and Polymer Example 1 are takenfrom the normalised cumulative heights shown in FIGS. 4 and 5respectively. Height measurements were taken at a data rate of 1 Hz, andsummed and normalised using Agilent GPC software.

TABLE 2 Comparative Polymer Example Polymer 1 1 Proportion of Proportionof total polymer total polymer Molecular weight by Triple weight byTriple weight Detection GPC Detection GPC range p/r ratio (%)(%) >1000000 >~1600 2.68 7.37 1000000-500000 ~1600-830 9.89 21.87 500000-300000  ~830-500 14.40 30.93  300000-100000  ~500-160 43.2939.70  100000-50000  ~160-80 16.73 0.13  50000-30000  ~80-50 5.36 0 <30000    ~50 7.66 0Comparison of the Hole-Transporting Polymers

The degree of insolubility of polymers was measured using the followingmethod.

A series of solutions of different concentration of the polymer in asolvent were prepared and the absorption of each was measured by UV-VISspectroscopy to provide a calibration curve. The polymer was thendeposited by spin coating onto glass substrates from solution to athickness of 22 nm as determined by a Dektak profilometer.

One of the substrates was left unbaked and the other was cross-linked byheating at 175° C. for 60 minutes. The cross-linked film was then soakedin a measured volume of solvent for a specified time, after which thesolvent was transferred to a cuvette and the absorption spectrummeasured by UV-VIS spectroscopy and compared to the calibration curve todetermine the concentration of polymer in solution. The non-cross-linkedfilm was treated similarly, which resulted in complete dissolution ofthe polymer. Measurement of absorption spectrum of this solution of thissample by UV-VIS spectroscopy gave the total amount of polymer present.

The amount of hole-transporting layer that remained insoluble aftercross-linking of the comparative hole-transporting polymer andhole-transporting polymer 1 respectively were compared in the tablebelow:

% of original material remaining Comparative hole-transporting  80polymer Hole-transporting polymer 100 (at limit of example 1 measurementtechnique)Comparative Device

A device having the following structure was prepared:

ITO/HIL/HTL/LE/Cathode ITO/HIL/HTL/LEL/Cathodewherein ITO is an indium-tin oxide anode; HIL is a hole-injecting layercomprising a hole-injecting material, HTL is a hole-transporting layer,and LEL is a light-emitting layer.

A substrate carrying ITO patterned to form pixel anodes was cleanedusing UV/Ozone. A layer of photoresist was deposited over the substrateby spin-coating and patterned to expose the pixel anodes and form wellshaving the pixel anodes at a base of the wells. A 30 nm hole-injectionlayer was formed by inkjet printing a hole-injection material into thewells. The hole-transporting layer was formed to a thickness of about 22nm by inkjet printing a solution of the Comparative Hole-TransportingPolymer and evaporating the solvent. The hole-transporting layer washeated at 170° C. for 1 hour to crosslink the crosslinkable groups ofthe polymer. A light-emitting layer was formed to a thickness of about65 nm by inkjet printing a solution of a light-emitting polymer and anadditive polymer, the light-emitting polymer comprising fluorene repeatunits of formula (XIa), a repeat unit of formula (VIIIa), amine repeatunits of formula (Va-1) and (Va-3). The cathode was formed by depositinga layer of sodium fluoride of a thickness of about 2 nm, a layer ofsilver of about 100 nm thickness and a layer of aluminium of a thicknessof about 100 nm.

Device Example 1

A device was prepared as described for the Comparative Device exceptthat hole-transporting polymer example 1 was used in place of thecomparative hole-transporting polymer.

Device Example 1 has improved performance compared to the ComparativeDevice. As shown in FIG. 3, Device Example 1 has an improved devicelifetime compared to the Comparative Device.

Although the present invention has been described in terms of specificexemplary embodiments, it will be appreciated that variousmodifications, alterations and/or combinations of features disclosedherein will be apparent to those skilled in the art without departingfrom the scope of the invention as set forth in the following claims.

The invention claimed is:
 1. An OLED comprising a hole-transportinglayer and light-emitting layer, wherein the hole-transporting layercomprises a hole-transporting polymer, wherein no more than 5% of thepolystyrene equivalent polymer weight measured by gel permeationchromatography consists of chains with a molecular weight of less than50,000.
 2. The OLED according to claim 1, wherein the hole-transportinglayer comprises a hole-transporting polymer, wherein no more than 0.2%of the polystyrene equivalent polymer weight measured by gel permeationchromatography consists of chains with a molecular weight of less than50,000.
 3. The OLED according to claim 1, wherein no more than 10% ofthe polystyrene equivalent polymer weight measured by gel permeationchromatography consists of polymer chains with a molecular weight ofless than 100,000.
 4. An OLED comprising a hole-transporting layer andlight-emitting layer, wherein the hole-transporting layer comprises ahole-transporting polymer wherein no more than 10% of the polystyreneequivalent polymer weight measured by gel permeation chromatographyconsists of chains with a molecular weight of less than 100,000.
 5. TheOLED according to claim 4, wherein no more than 5% of the polystyreneequivalent polymer weight measured by gel permeation chromatographyconsists of chains with a molecular weight of less than 100,000.
 6. TheOLED according to claim 1, wherein more than 20% of the polystyreneequivalent polymer weight measured by gel permeation chromatographyconsists of polymer chains with a molecular weight of at least 300,000.7. An OLED comprising a hole-transporting layer and light-emitting layerwherein the hole-transporting layer comprises a hole-transportingpolymer, wherein no more than 5% of the weight of the polymer asmeasured by triple detection gel permeation chromatography consists ofpolymer chains with a p/r ratio of less than about 50 wherein p/r isabsolute polymer chain molecular weight/average repeat unit molecularweight.
 8. The OLED according to claim 7, wherein less than 1% of theweight of the polymer as measured by triple detection gel permeationchromatography consists of polymer chains with a p/r ratio of less thanabout
 50. 9. The OLED according to claim 7, wherein less than 10%, ofthe weight of the polymer as measured by triple detection gel permeationchromatography consists of polymer chains with a p/r ratio of less thanabout
 100. 10. The OLED according to claim 7, wherein more than 20% ofthe weight of the polymer as measured by triple detection gel permeationchromatography consists of polymer chains with a p/r ratio of more thanabout
 500. 11. The OLED according to claim 1, wherein thehole-transporting polymer has a polydispersity index of less than
 4. 12.The OLED according to claim 1, wherein the hole-transporting polymer hasa number-average molecular weight (Mn) in the range of 1×10⁵ to 1×10⁶.13. The OLED according to claim 1, wherein the hole-transporting polymerhas a weight average molecular weight in the range of 1×10⁵ to 1×10⁶.14. The OLED according to claim 1, wherein the hole-transporting polymeris crosslinked.
 15. The OLED according to claim 14, wherein no more than25 mol % of the repeat units of the hole-transporting polymer arecrosslinking groups.
 16. The OLED according to claim 1, wherein thehole-transporting polymer is a conjugated polymer.
 17. The OLEDaccording to claim 1, wherein the hole-transporting polymer comprises arepeat unit of formula (V):

wherein Ar⁸ and Ar⁹ in each occurrence are independently substituted orunsubstituted aryl or heteroaryl, g is greater than or equal to 1, R¹³is H or a substituent, and c and d are each independently 1, 2, or 3.18. The OLED according to claim 1, wherein the hole-transporting polymeris a fractionated polymer.
 19. A process for the preparation of an OLEDaccording to claim 1, comprising the steps of: (i) forming ahole-transporting layer which comprises the hole-transporting polymer;and (ii) forming a light-emitting layer over the hole transportinglayer, wherein the light-emitting layer is formed by depositing aformulation comprising the material or materials of said layer and atleast one solvent, and evaporating the at least one solvent.
 20. Theprocess according to claim 19, wherein the hole-transporting layer isformed by depositing a formulation comprising the material or materialsof said layer and at least one solvent, and evaporating the at least onesolvent.
 21. The process according to claim 20, wherein thehole-transporting polymer is soluble in one or more solvents used instep (ii) in forming the light-emitting layer.
 22. The process accordingto claim 19, wherein the hole-transporting layer is crosslinked prior toformation of the light-emitting layer.